145381-23-3Relevant articles and documents
[RuCl2(η6-p-cymene)] complexes bearing phosphinous acid ligands: Preparation, application in C-H bond functionalization and mechanistic investigations
Graux, Lionel V.,Giorgi, Michel,Buono, Gérard,Clavier, Hervé
, p. 6491 - 6502 (2016)
A series of [RuCl2(η6-p-cymene)] complexes bearing phosphinous acid (PA) ligands have been straightforwardly prepared from the dimer [RuCl2(p-cymene)]2 and secondary phosphine oxides (SPOs) and fully characteriz
A most user-friendly protocol for ring closing metathesis reactions
Fuerstner, Alois,Ackermann, Lutz
, p. 95 - 96 (1999)
Ring closing metathesis reactions (RCM) can be conveniently achieved in a photo-assisted manner simply by heating a solution of the diene substrate, catalytic amounts of commercially available [(p-cymene)RuCl2]2 4 and PCy3
Ruthenium-Catalyzed Regioselective 1,4-Hydroboration of Pyridines
Kaithal, Akash,Chatterjee, Basujit,Gunanathan, Chidambaram
, p. 3402 - 3405 (2016)
Simple ruthenium precursor [Ru(p-cymene)Cl2]2 1 catalyzed regioselective 1,4-dearomatization of pyridine derivatives using pinacolborane is reported. Two catalytic intermediates, [Ru(p-cymene)Cl2Py] 2 and [Ru(p-cymene)Cls
Ruthenium-Catalyzed Reductive Cleavage of Unstrained Aryl-Aryl Bonds: Reaction Development and Mechanistic Study
Zhu, Jun,Chen, Peng-hao,Lu, Gang,Liu, Peng,Dong, Guangbin
supporting information, p. 18630 - 18640 (2019/11/21)
Cleavage of carbon-carbon bonds has been found in some important industrial processes, for example, petroleum cracking, and has inspired development of numerous synthetic methods. However, nonpolar unstrained C(aryl)-C(aryl) bonds remain one of the toughest bonds to be activated. As a detailed study of a fundamental reaction mode, here a full story is described about our development of a Ru-catalyzed reductive cleavage of unstrained C(aryl)-C(aryl) bonds. A wide range of biaryl compounds that contain directing groups (DGs) at 2,2′ positions can serve as effective substrates. Various heterocycles, such as pyridine, quinoline, pyrimidine, and pyrazole, can be employed as DGs. Besides hydrogen gas, other reagents, such as Hantzsch ester, silanes, and alcohols, can be employed as terminal reductants. The reaction is pH neutral and free of oxidants; thus a number of functional groups are tolerated. Notably, a one-pot C-C activation/C-C coupling has been realized. Computational and experimental mechanistic studies indicate that the reaction involves a ruthenium(II) monohydride-mediated C(aryl)-C(aryl) activation and the resting state of the catalyst is a η4-coordinated ruthenium(II) dichloride complex, which could inspire development of other transformations based on this reaction mode.
Homobimetallic ruthenium-arene complexes bearing vinylidene ligands: Synthesis, characterization, and catalytic application in olefin metathesis
Borguet, Yannick,Sauvage, Xavier,Zaragoza, Guillermo,Demonceau, Albert,Delaude, Lionel
, p. 6675 - 6686 (2011/03/16)
Five new arylvinylidene complexes with substituents ranging from electron-donating to strongly withdrawing (p-OMe, p-Me, p-Cl, p-CF3, and m-(CF3)2) were isolated in high yields by reacting [(p-cymene)Ru(μ-Cl)3RuCl(η2 C2H 4)(PCy3)] (3) with the corresponding phenylacetylene derivatives. The known phenylvinylidene complex [(p-cymene)Ru(μ-Cl) 3RuCl(=C=CHPh)(PCy3)] (5) was also obtained from [RuCl2(p-cymene)]2, tricyclohexylphosphine, and phenylacetylene under microwave irradiation. The influence of the remote aryl substituents on structural features was investigated by IR, NMR, and XRD spectroscopies. A very good linear relationship was observed between the chemical shift of the vinylidene α-carbon atom and the Hammett σ-constants of the aryl group substituents. The catalytic activity of the six homobimetallic complexes was probed in various types of olefin metathesis reactions. Unsubstituted phenylvinylidene compound 5 served as a lead structure for these experiments. Its reaction with norbornene afforded high molecular weight polymers with a broad polydispersity index and mostly trans double bonds. Aluminum chloride was a suitable cocatalyst for the ring-opening metathesis polymerization of cyclooctene and led to the formation of high molecular weight polyoctenamer with a rather narrow polydispersity index (Mw/M n = 1.25) and an almost equimolar proportion of cis and trans double bonds. No major changes were observed in the polymer yields and microstructures when complexes bearing donor groups on their aryl rings were employed as catalyst precursors. On the other hand, compounds bearing strongly electron-withdrawing substituents were significantly less active. Model vinylidene compound 5 and its ruthenium-ethylene parent (3) both required the addition of phenylacetylene to achieve the ring-closing metathesis of diethyl 2,2-diallylmalonate. Thus, the role of this terminal alkyne cocatalyst goes beyond the facile replacement of the η2-alkene ligand with a vinylidene fragment.
Multifaceted chemistry of [(Cymene)RuCl2]2 and PCy3
Solari, Euro,Gauthier, Sebastien,Scopelliti, Rosario,Severin, Kay
, p. 4519 - 4526 (2009/12/06)
The reaction of [(cymene)RuCl2]2 (1) with PCy 3 was investigated using different stoichiometries and reaction conditions. Whereas a mixture of complex 1 and 2 equiv of PCy3 in methanol gave the known adduct [(cy
Novel ruthenium(II) N-heterocyclic carbene complexes as catalyst precursors for the Ring-Opening Metathesis Polymerization (ROMP) of enantiomerically pure monomers: X-ray structures, reactivity, and quantum chemical considerations
Buchmeiser, Michael R.,Wang, Dongren,Zhang, Yan,Naumov, Sergej,Wurst, Klaus
, p. 3988 - 4000 (2008/03/12)
Four chiral, enantiomerically pure monomers, exo,exo-N,N-(norborn-5-ene-2, 3-dicarbimido)-L-valine ethyl ester (exo-1), endo,endo-N,N-(norborn-5-ene-2,3- dicarbimido)-L-valine ethyl ester (endo-1), exo,exo-N,N-(norborn-5-ene-2,3- dicarbimido)-L-valine-ferr-butylamide (exo-2), and endo,endo-N,N-(norborn-5-ene- 2,3-dicarbimido)-L-valine-tert-butylamide (endo-2), were subjected to ring-opening metathesis polymerization (ROMP) with Ru(CF3CO 2)2(IMesH2)(p-cymene) (3), Ru(CF 3CO2)2(IMes)(p-cymene) (4), RuCl 2(IMes)-(p-cymene) (5), Ru(PCy3)(CF3CO 2)2(p-cymene) (6), Ru(CF3CO2) 2(p-cymene)·CF3COOAgPCy3(6a),Ru(CF 3CO2)2-(PPh3)(p-cymene) (7), Ru(CF3CO2)2(IMes)(PhNC)3 (8), and Ru(CF3CO2)2(IMesH2)(PhNC) 3 (9) (IMes = 1,3-dimesitylimidazol-2-ylidene, IMesH2 = 1,4-dimesityl-4,5-diyhdroimidazolin-2-ylidene, PCy3 = tricyclohexylphosphane). X-ray structures of precatalysts 3 and 6-9 are presented. Compounds 3 and 4 displayed significant ROMP activity, allowing for the controlled, yet nonliving synthesis of the corresponding polymers with polydispersity indices (PDIs) in the range of 1.17-2.14. In all cases the exo isomers of compounds 1 and 2 were polymerized by preference. While poly(endo-1) was formed in an all-trans form, poly(exo-1) and poly(exo-2) were produced in their cis/trans forms with a cis content of around 40%. Calculations carried out at the B3LYP/LACVP* level suggest two possible mechanisms for the increased reactivity of the 2,3-R2-exo,exo isomers of norborn-5-ene-2,3-dicarbimido derivatives resulting in the formation of the ROMP-active RuIV alkylidene. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Efficient total syntheses of resin glycosides and analogues by ring-closing olefin metathesis
Fuerstner, Alois,Mueller, Thomas
, p. 7814 - 7821 (2007/10/03)
A highly efficient entry into the resin glycoside family of natural products is outlined which takes advantage of the inherently modular character of ring-closing metathesis (RCM) for the formation of their macrolactone substructures. Starting from only t
